Textbook-Integrated Guide to Educational Resources

TIGER

Experimental Design and Optimization: Application to a Grignard ReactionNaoual Bouzidi and Christel GozziThis 5-week project, which systematically investigates optimizing the synthesis of benzyl-1-cyclopentan-1-ol, constitutes an initiation into research methodology and experimental design to prepare the student-engineer for an industry internship. Other pedagogical goals include experience in synthetic techniques, obtaining reproducible yields, and using quantitative analysis methods.Bouzidi, Naoual; Gozzi, Christel. J. Chem. Educ.2008, 85, 1544.

Addition Reactions |

Alcohols |

Aldehydes / Ketones |

Chemometrics |

Gas Chromatography |

Organometallics |

Synthesis

Evaluating Mechanisms of Dihydroxylation by Thin-Layer ChromatographyBenjamin T. Burlingham and Joseph C. RettigPresents a microscale experiment in which cyclohexene is dihydroxylated under three sets of conditions and the products determined through thin-layer chromatography. Teams of students evaluate proposed mechanisms for each dihydroxylation in light of the data collected.Burlingham, Benjamin T.; Rettig, Joseph C. J. Chem. Educ.2008, 85, 959.

Regioselectivity in Organic Synthesis: Preparation of the Bromohydrin of α-MethylstyreneBrad Andersh, Kathryn N. Kilby, Meghan E. Turnis, and Drew L. MurphyIn the described experiment, the regiochemical outcome of the addition of "HOBr" to a-methylstyrene is investigated. Although both "classic" qualitative analysis and instrumental techniques are described, the emphasis of this experiment is on the utilization 13C and DEPT-135 NMR spectroscopy to determine the regiochemical outcome of the addition. Andersh, Brad; Kilby, Kathryn N.; Turnis, Meghan E.; Murphy, Drew L. J. Chem. Educ.2008, 85, 102.

Addition Reactions |

Alcohols |

Alkenes |

Constitutional Isomers |

IR Spectroscopy |

Microscale Lab |

NMR Spectroscopy |

Synthesis

A Discovery-Based Experiment Involving Rearrangement in the Conversion of Alcohols to Alkyl HalidesRichard A. Kjonaas and Ryand J. F. TuckerThis article reports a discovery-based experiment in which students convert three alcohols to alkyl halides under acidic conditions and record the 13C NMR spectrum in each case. By comparing the number of resonances observed with the number of resonances predicted for each possible product, students draw several conclusions about the resulting rearrangement.Kjonaas, Richard A.; Tucker, Ryand J. F. J. Chem. Educ.2008, 85, 100.

Alcohols |

Carbocations |

Gas Chromatography |

NMR Spectroscopy |

Nucleophilic Substitution

Hydration of Acetylene: A 125th AnniversaryDmitry A. Ponomarev and Sergey M. ShevchenkoThe discovery the hydration of alkynes catalyzed by mercury ions by Mikhail Kucherov made possible industrial production of acetaldehyde from acetylene and had a profound effect on the development of industrial chemistry in the 1920th centuries.Ponomarev, Dmitry A.; Shevchenko, Sergey M. J. Chem. Educ.2007, 84, 1725.

Addition Reactions |

Aldehydes / Ketones |

Alkynes |

Catalysis |

Industrial Chemistry |

Reactions

An Improved Method for Studying the Enzyme-Catalyzed Oxidation of Glucose Using Luminescent ProbesWilliam D. Bare, Chi V. Pham, Matthew Cuber, and J. N. DemasA new method is presented for measuring the rate of glucose oxidation in the presence of glucose oxidase that employs a low-cost fluorescence instrument to directly determine the concentration of oxygen in real time, thus obviating complicated reaction schemes. The method can also be used to investigate specificity and inhibition.Bare, William D.; Pham, Chi V.; Cuber, Matthew; Demas, J. N. J. Chem. Educ.2007, 84, 1511.

Carbocations |

Coordination Compounds |

Enzymes |

Fluorescence Spectroscopy |

Spectroscopy |

Instrumental Methods |

Carbohydrates |

Kinetics

Synthesis of Anomeric Methyl Fructofuranosides and Their Separation on an Ion-exchange ResinErkki Nurminen, Päivi Poijärvi, Katja Koskua, and Jari HovinenTreatment of d-fructose with methanol in the presence of acid as a catalyst gives a mixture of methyl--d-fructopyranoside, methyl-a-D-fructofuranoside, and methyl--d- fructofuranoside, which are separated on an ion exchange column and characterized polarimetrically.Nurminen, Erkki; Poijärvi, Päivi; Koskua, Katja; Hovinen, Jari. J. Chem. Educ.2007, 84, 1480.

Carbocations |

Chirality / Optical Activity |

Chromatography |

Ion Exchange |

NMR Spectroscopy |

Synthesis |

Thin Layer Chromatography |

Carbohydrates

A Guided-Inquiry Approach to the Sodium Borohydride Reduction and Grignard Reaction of Carbonyl CompoundsRobert E. RosenbergStudents teams identify unknowns and their reaction products and use their data to deduce that esters are less electrophilic than the other carbonyl compounds present, that Grignard reagents are more nucleophilic than sodium borohydride, and that carboxylic acid derivatives do not undergo the nucleophilic addition reactions that are characteristic of aldehydes and ketones. Rosenberg, Robert E. J. Chem. Educ.2007, 84, 1474.

Addition Reactions |

Aldehydes / Ketones |

Esters |

Grignard Reagents |

IR Spectroscopy |

Oxidation / Reduction |

Reactions |

Student-Centered Learning

Reaction-Map of Organic ChemistrySteven MurovThe Reaction-Map of Organic Chemistry has been designed to provide an overview of most of the reactions needed for the organic chemistry course and should help students develop synthetic routes from one functional group to another.Murov, Steven. J. Chem. Educ.2007, 84, 1224.

Markovnikov's RuleRobert C. KerberThe use of Markovniknov and anti-Markovnikov to describe addition reactions and their products has long outlived its utility.Kerber, Robert C. . J. Chem. Educ.2007, 84, 1109.

Addition Reactions |

Reactions |

Mechanisms of Reactions

Markovnikov's RuleRobert C. KerberThe use of Markovniknov and anti-Markovnikov to describe addition reactions and their products has long outlived its utility.Kerber, Robert C. . J. Chem. Educ.2007, 84, 1109.

Addition Reactions |

Reactions |

Mechanisms of Reactions

The Aldol Addition and Condensation: The Effect of Conditions on Reaction PathwayR. David Crouch, Amie Richardson, Jessica L. Howard, Rebecca L. Harker, and Kathryn H. BarkerDescribes an experiment offering the opportunity for students to observe the critical role that reaction temperature and base strength have in determining the product of the base-mediated addition of a ketone to an aldehyde.Crouch, R. David; Richardson, Amie; Howard, Jessica L.; Harker, Rebecca L.; Barker, Kathryn H. J. Chem. Educ.2007, 84, 475.

Was Markovnikov's Rule an Inspired Guess?Peter HughesA study of 19th century literature shows that neither Markovnikov nor any of his contemporaries carried out the reactions often attributed to himthe addition of hydrogen bromide or hydrogen chloride to propene. Since there is little evidence for Markovnikov's rule in his 1870 article, it is likely that it was more of an inspired guess than a rational conclusion.Hughes, Peter. J. Chem. Educ.2006, 83, 1152.

Addition Reactions |

Alkenes |

Mechanisms of Reactions

Rapid and Stereoselective Conversion of a trans-Cinnamic Acid to a β-BromostyreneThomas A. EvansThe stereoselective synthesis of an aryl vinyl bromide is accomplished in a rapid microscale reaction of trans-4-methoxycinnamic acid with N-bromosuccinimide in dichloromethane. This guided-inquiry experiment links reactivity, stereochemistry, and mechanism in electrophilic addition reactions of alkenes and in E1 and E2 elimination reactions that form alkenes.Evans, Thomas A. J. Chem. Educ.2006, 83, 1062.

Diels–Alder Synthesis of endo-cis-N-Phenylbicyclo[2.2.2]oct-5-en-2,3-dicarboximideMarsha R. Baar and Kristin Wustholzendo-cis-N-Phenylbicyclo[2.2.2]oct-5-en-2,3-dicarboximide was synthesized by a DielsAlder cycloaddition of 1,3-cyclohexadiene and N-phenylmaleimide in ethyl acetate. 1,3-Cyclohexadiene and N-phenylmaleimide were selected to illustrate the Alder rule, which reflects a preference for endo products and to overcome the difficulties associated with the traditional combination of 1,3-cyclopentadiene and maleic anhydride. Baar, Marsha R.; Wustholz, Kristin. J. Chem. Educ.2005, 82, 1393.

Asymmetric Synthesis |

Microscale Lab |

Stereochemistry |

Addition Reactions |

Alkenes |

IR Spectroscopy |

NMR Spectroscopy

The Addition of Bromine to 1,2-Diphenylethene Judith C. Amburgey-Peters and LeRoy W. HaynesWe investigated the reaction of (Z)-1,2-diphenylethene (cis-stilbene) with various brominating reagents and solvents following directions in standard organic chemistry manuals. We were particularly interested in learning which combination of brominating reagent and solvent gave the best yield of (d,l)-1,2-dibromo-1,2-diphenylethane without the formation of significant amounts of meso-1,2-dibromo-1,2-diphenylethane, which is essentially the sole product from the reaction of bromine with (E)-1,2-diphenylethene (trans-stilbene). Based on the results from the standard preparatory methods, some permutations of solvent and brominating reagent were tried.Amburgey-Peters, Judith C.; Haynes, LeRoy W. J. Chem. Educ.2005, 82, 1051.

"You're Repulsive!"Teaching VSEPR in a Not-So-Elegant WayRobert S. H. LiuValence shell electron pair repulsive (VSEPR) interaction is an important concept particularly in discussing structural properties of molecules. In this article we showed five organic examples not commonly associated with VSEPR but yet all involving repulsive interactions of valence electrons, which provides ready explanations for altered chemical reactivity and spectroscopic properties of organic compounds. The ready catchy phrase Youre Repulsive! is the common thread used throughout these five examples.Liu, Robert S. H. J. Chem. Educ.2005, 82, 558.

Mechanisms of Reactions |

UV-Vis Spectroscopy |

Reactions |

Addition Reactions |

Electrophilic Substitution

Green Chemistry Laboratory: Benign Synthesis of 4,6-Diphenyl[2,2']bipyridine via Sequential Solventless Aldol and Michael Addition ReactionsGareth W. V. Cave and Colin L. RastonSolventless reaction methodology avoids the use of hazardous and toxic solvents and minimizes generation of waste, thereby addressing some of the principles of green chemistry. 2,4,6-Trisubstituted pyridines are readily prepared in high yield using this methodology in three steps: (i) solventless aldol condensation of benzaldehyde and acetophenone, (ii) solventless Michael addition of 2-acetylpyridine to the previously formed 1,3-diphenylpropenone, and (iii) the ring closure of the resulting 1,5-diketone in acetic acid with ammonium acetate.Cave, Gareth W. V.; Raston, Colin L. J. Chem. Educ.2005, 82, 468.

Green Chemistry |

IR Spectroscopy |

NMR Spectroscopy |

Synthesis |

Addition Reactions

The Evolution of a Green Chemistry Laboratory Experiment: Greener Brominations of StilbeneLallie C. McKenzie, Lauren M. Huffman, and James E. HutchisonWe describe two new greener alkene bromination reactions that offer enhanced laboratory safety and convey important green chemistry concepts, in addition to illustrating the chemistry of alkenes. The two alternative reactions, one involving pyridinium tribromide and a second using hydrogen peroxide and hydrobromic acid, are compared to the traditional bromination of stilbene through the application of green metrics, including atom economy, percent experimental atom economy, E factor, and effective mass yield.McKenzie, Lallie C.; Huffman, Lauren M.; Hutchison, James E. J. Chem. Educ.2005, 82, 306.

Synthesis |

Green Chemistry |

Aromatic Compounds |

Addition Reactions |

Alkenes

The Sharpless Asymmetric Dihydroxylation in the Organic Chemistry Majors LaboratoryChristopher J. Nichols and Melissa R. TaylorA six-period laboratory exercise has been developed that uses the convenient Sharpless asymmetric dihydroxylation (AD) to illustrate the principles of a chiral synthesis. Using one particular alkene, students perform a racemic dihydroxylation, an AD using a commercially available AD-mix, and then an AD using an ester derivative of dihydroquinidine that they synthesized themselves. The structures of the products are confirmed with 1H NMR spectroscopy and the enantiomeric excesses of the diols are determined using a chiral GC column. Nichols, Christopher J.; Taylor, Melissa R. J. Chem. Educ.2005, 82, 105.

Mechanism Templates: Lecture Aids for Effective Presentation of Mechanism in Introductory Organic ChemistryBrian J. McNelisTo promote active student learning of mechanism in introductory organic chemistry, hand-outs have been developed with incomplete structures for reaction processes depicted, which are called mechanism templates. The key to these lecture aids is to provide only enough detail in the diagram to facilitate notetaking, ensuring that these templates are dynamic learning tools that must be utilized by an engaged and alert student.Brian J. McNelis. J. Chem. Educ.1998, 75, 479.

Learning Theories |

Mechanisms of Reactions |

Reactions |

Addition Reactions |

Acids / Bases |

Electrophilic Substitution |

Nucleophilic Substitution

A -78°C Sequential Michael Addition for the Organic LabMichael W. TanisThis paper introduces a cold-temperature enolate alkylation reaction that can be performed safely and inexpensively by undergraduate students in approximately two 3-hour lab sessions. Tanis, Michael W. J. Chem. Educ.1997, 74, 112.

Addition Reactions |

Alkenes |

Aldehydes / Ketones |

Synthesis

Carbonyl and Conjugate Additions to Cyclohexenone: Experiments Illustrating Reagent SelectivityMichael G. Organ and Paul AndersonUndergraduate students leaving an organic chemistry program should have exposure to these concepts and hands-on experience in dealing practically with the issue of selectivity. In this paper, selective addition of a nucleophile to either end of the enone moiety in cyclohexenone is examined. Organ, Michael G.; Anderson, Paul. J. Chem. Educ.1996, 73, 1193.

Reaction of bromine with hydrocarbons on the overhead, real or simulatedSolomon, Sally; Gregory, Michael; Padmanabhan, Sandeep; Smith, KurtA simulation that looks like the addition of bromine to hydrocarbons but is not (the bromine is simulated using a mixture of food colorings).Solomon, Sally; Gregory, Michael; Padmanabhan, Sandeep; Smith, Kurt J. Chem. Educ.1990, 67, 961.

Concertedness of 1,3-dipolar cycloadditionsHaque, M. SerajulThe 1,3-dipolar cycloaddition is the union of a 1,3-dipole with a multiple bond system (a dipolarophile) to form a five-membered ring; the process is regarded as one of the most general methods for the synthesis of five-membered heterocycles.Haque, M. Serajul J. Chem. Educ.1984, 61, 490.

Addition Reactions |

Alkanes / Cycloalkanes |

Mechanisms of Reactions |

Heterocycles |

Synthesis |

MO Theory

Who is anti-Markovnikov?Tedder, J. M.What are the factors that control the rate and orientation of free radical addition to alkenes?Tedder, J. M. J. Chem. Educ.1984, 61, 237.

Stereospecific thermal cycloadditions and catalyzed isomerizations: An organic laboratory projectPasto, D. J.; Duncan, J. A.; Silversmith, E. F.The authors have prepared a sequence of experiments for their undergraduate organic chemistry laboratory concerned with the preparation of cis and trans 1,4-diphenyl-2-butene-1,4diones, their cycloadditions reactions with cyclopentandiene, and with related isomerization reactions of both the sequence, which has met with much success experimentally, clearly and collectively demonstrates certain aspects of the concepts of thermodynamics, kinetics, and stereochemistry and photochemistry.Pasto, D. J.; Duncan, J. A.; Silversmith, E. F. J. Chem. Educ.1974, 51, 277.

Photochemistry |

Constitutional Isomers |

Addition Reactions

Stereochemistry of carbonyl addition reactionsGoller, Edwin J.This article is a brief summary of some of the more important unifying concepts that have been proposed in the study of the stereo chemistry of carbonyl addition reactions.Goller, Edwin J. J. Chem. Educ.1974, 51, 182.

Donor-acceptor interactions in organic chemistrySunderwirth, S. G.The purpose of this article is to aid teachers in making even more effective use of theoretical considerations in teaching organic chemistry; the primary objective is to emphasize the underlying principles that are common to the following four basic types of reactions: substitution, addition, elimination, and rearrangement.Sunderwirth, S. G. J. Chem. Educ.1970, 47, 728.

Stable gaseous species at high temperaturesSiegel, BernardPresents a systematic correlation of the bonding in the gaseous elements with the strengths of their respective bonds.Siegel, Bernard J. Chem. Educ.1963, 40, 304.